US5068371A - Novel nitrogen-containing titanocenes, and the use thereof - Google Patents

Novel nitrogen-containing titanocenes, and the use thereof Download PDF

Info

Publication number
US5068371A
US5068371A US07/527,989 US52798990A US5068371A US 5068371 A US5068371 A US 5068371A US 52798990 A US52798990 A US 52798990A US 5068371 A US5068371 A US 5068371A
Authority
US
United States
Prior art keywords
alkyl
bis
phenyl
substituted
cyclopentadienyl
Prior art date
Legal status (The legal status is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the status listed.)
Expired - Fee Related
Application number
US07/527,989
Other languages
English (en)
Inventor
Eginhard Steiner
Harry Beyeler
Rinaldo Husler
Current Assignee (The listed assignees may be inaccurate. Google has not performed a legal analysis and makes no representation or warranty as to the accuracy of the list.)
BASF Corp
Original Assignee
Ciba Geigy Corp
Priority date (The priority date is an assumption and is not a legal conclusion. Google has not performed a legal analysis and makes no representation as to the accuracy of the date listed.)
Filing date
Publication date
Application filed by Ciba Geigy Corp filed Critical Ciba Geigy Corp
Assigned to CIBA-GEIGY CORPORATION reassignment CIBA-GEIGY CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST. Assignors: BEYELER, HARRY, HUSLER, RINALDO, STEINER, EGINHARD
Application granted granted Critical
Publication of US5068371A publication Critical patent/US5068371A/en
Assigned to CIBA SPECIALTY CHEMICALS CORPORATION reassignment CIBA SPECIALTY CHEMICALS CORPORATION ASSIGNMENT OF ASSIGNORS INTEREST (SEE DOCUMENT FOR DETAILS). Assignors: CIBA-GEIGY CORPORATION
Anticipated expiration legal-status Critical
Expired - Fee Related legal-status Critical Current

Links

Classifications

    • C—CHEMISTRY; METALLURGY
    • C08—ORGANIC MACROMOLECULAR COMPOUNDS; THEIR PREPARATION OR CHEMICAL WORKING-UP; COMPOSITIONS BASED THEREON
    • C08F—MACROMOLECULAR COMPOUNDS OBTAINED BY REACTIONS ONLY INVOLVING CARBON-TO-CARBON UNSATURATED BONDS
    • C08F2/00—Processes of polymerisation
    • C08F2/46—Polymerisation initiated by wave energy or particle radiation
    • C08F2/48—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light
    • C08F2/50—Polymerisation initiated by wave energy or particle radiation by ultraviolet or visible light with sensitising agents
    • C—CHEMISTRY; METALLURGY
    • C07—ORGANIC CHEMISTRY
    • C07F—ACYCLIC, CARBOCYCLIC OR HETEROCYCLIC COMPOUNDS CONTAINING ELEMENTS OTHER THAN CARBON, HYDROGEN, HALOGEN, OXYGEN, NITROGEN, SULFUR, SELENIUM OR TELLURIUM
    • C07F17/00—Metallocenes
    • G—PHYSICS
    • G03—PHOTOGRAPHY; CINEMATOGRAPHY; ANALOGOUS TECHNIQUES USING WAVES OTHER THAN OPTICAL WAVES; ELECTROGRAPHY; HOLOGRAPHY
    • G03F—PHOTOMECHANICAL PRODUCTION OF TEXTURED OR PATTERNED SURFACES, e.g. FOR PRINTING, FOR PROCESSING OF SEMICONDUCTOR DEVICES; MATERIALS THEREFOR; ORIGINALS THEREFOR; APPARATUS SPECIALLY ADAPTED THEREFOR
    • G03F7/00—Photomechanical, e.g. photolithographic, production of textured or patterned surfaces, e.g. printing surfaces; Materials therefor, e.g. comprising photoresists; Apparatus specially adapted therefor
    • G03F7/004—Photosensitive materials
    • G03F7/027—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds
    • G03F7/028—Non-macromolecular photopolymerisable compounds having carbon-to-carbon double bonds, e.g. ethylenic compounds with photosensitivity-increasing substances, e.g. photoinitiators
    • G03F7/029—Inorganic compounds; Onium compounds; Organic compounds having hetero atoms other than oxygen, nitrogen or sulfur
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/12—Nitrogen compound containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/12—Nitrogen compound containing
    • Y10S430/121—Nitrogen in heterocyclic ring
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/122—Sulfur compound containing
    • Y—GENERAL TAGGING OF NEW TECHNOLOGICAL DEVELOPMENTS; GENERAL TAGGING OF CROSS-SECTIONAL TECHNOLOGIES SPANNING OVER SEVERAL SECTIONS OF THE IPC; TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10—TECHNICAL SUBJECTS COVERED BY FORMER USPC
    • Y10S—TECHNICAL SUBJECTS COVERED BY FORMER USPC CROSS-REFERENCE ART COLLECTIONS [XRACs] AND DIGESTS
    • Y10S430/00—Radiation imagery chemistry: process, composition, or product thereof
    • Y10S430/1053—Imaging affecting physical property or radiation sensitive material, or producing nonplanar or printing surface - process, composition, or product: radiation sensitive composition or product or process of making binder containing
    • Y10S430/1055—Radiation sensitive composition or product or process of making
    • Y10S430/114—Initiator containing
    • Y10S430/122—Sulfur compound containing
    • Y10S430/123—Sulfur in heterocyclic ring

Definitions

  • the present invention relates to titanocenes containing fluoroaryl radicals which are substituted by pyrrylalkyl groups or amidoalkyl groups, to a process for the preparation thereof and to the use thereof as photoinitiators for the photopolymerization of ethylenically unsaturated compounds.
  • U.S. Pat. No. 4,590,287 discloses that titanocenes containing fluoroaryl ligands are excellent photoinitiators.
  • the fluoroaryl radicals of these titanocenes may carry further substituents, including amino groups and aminoalkyl groups.
  • U.S. Pat. No. 4,857,654 discloses titanocenes having polyoxaalkylene chains on the fluoroaryl ligands.
  • EP-A-256,981 describes titanocenes containing silylated cyclopentadienyl radicals.
  • EP-A-318,894 discloses titanocenes having pyrrole substituents on the fluoroaryl ligands
  • EP-A-318,893 describes titanocenes having nitrogen-containing ligands on the fluoroaryl radical
  • U.S. Pat. No. 4,713,401 discloses titanocenes which have CF 3 substituents in place of fluorine atoms on the aryl ligands.
  • Titanocenes containing fluoroaryl radicals which are substituted by pyrrylalkyl groups, amidoalkyl groups or imidoalkyl groups have hitherto not been disclosed. However, it has been shown that titanocenes substituted in this manner are likewise excellent photoinitiators.
  • the invention relates to titanocenes of the formula I ##STR2## in which both the R 1 radicals, independently of one another, are cyclopentadienyl.sup. ⁇ , indenyl.sup. ⁇ or 4,5,6,7-tetrahydroindenyl.sup. ⁇ , each of which is unsubstituted, monosubstituted or polysubstituted by C 1 -C 18 alkyl, C 1 -C 18 alkoxy, C 2 -C 18 alkenyl, C 5 -C 8 cycloalkyl, C 6 -C 16 aryl, C 7 -C 16 aralkyl, -Si(R 4 ) 3 , -Ge(R 4 ) 3 , cyano or halogen, and R 4 is C 1 -C 12 alkyl, C 5 -C 12 cycloalkyl, C 6 -C 10 aryl or C 7 -C 16 aralkyl, R 2 is
  • R 5 and R 6 and/or R 7 and R 8 or R 6 and R 7 are each together --(CH 2 ) 3 --, --(CH 2 ) 4 --, --CH ⁇ CH--CH ⁇ CH--, --CH ⁇ CH--C(R 12 ) ⁇ CH--, --CH 2 OCH 2 -- or --CH 2 N(C 1 -C 4 alkyl)CH 2 --, in which R 12 is hydroxyl, C 1 -C 4 alkoxy or C 2 -C 4 alkanoyloxy, Y is a --CO--, --CS--, --COO--, --SO 2 -- or --Si(R 4 ) 2 -- group, R 9 is hydrogen, linear or branched C 1 -C 20 alkyl, C 2 -C 20 alkenyl, C 3
  • R 1 groups are preferably identical radicals.
  • Suitable substituents for R 1 are: linear or branched alkyl or alkoxy having 1 to 18, particularly 1 to 12 and in particular 1 to 6, C atoms, and alkenyl having 2 to 18, particularly 2 to 12, and in particular 2 to 6, C atoms, for example methyl, ethyl, propyl, isopropyl, n-butyl, tert.-butyl, pentyl, hexyl, octyl, decyl, dodecyl, tetradecyl, hexadecyl, octadecyl and corresponding alkenyl and alkoxy groups; cycloalkyl having 5 to 8 ring carbon atoms, for example cyclopentyl, cyclohexyl, cycloheptyl, methylcyclopentyl and methylcyclohexyl; aryl having 6 to 10 C atoms and
  • alkyl R 4 examples are methyl, ethyl, n- and i-propyl, n-, i- and t-butyl, pentyl, hexyl, heptyl and octyl.
  • the radicals R 1 may contain up to 5, but particularly up to 3 substituents. Both R 1 groups are preferably cyclopentadienyl.sup. ⁇ or methylcyclopentadienyl.sup. ⁇ radicals, in particular cyclopentadienyl.sup. ⁇ radicals.
  • R 2 as a 6-membered carbocyclic, aromatic and fluorine-substituted ring may be fluorine-substituted indene, indane, fluorene, naphthalene and, particularly, phenyl.
  • R 2 as a heterocyclic, aromatic and 5-membered radical preferably contains one hetero atom and as a 6-membered ring preferably contains 1 or 2 hetero atoms.
  • both ortho-positions are substituted by fluorine.
  • Examples are 4,6-difluoroinden-5-yl, 5,7-difluoroindan-6-yl, 2,4-difluorofluoren-3-yl, 1,3-difluoronaphth-2-yl, 2,6-difluorophen-1-yl, 2,4-difluoropyrr-3-yl, 2,4-difluorofur-3-yl, 2,4-difluorothien-3-yl, 2,4-difluoropyrid-3-yl, 4,6-difluoropyrimidin-5-yl and 3,5-difluoropyridazin-4-yl.
  • R 2 in the formula I is substituted 2,6-difluorophen-1-yl.
  • R 2 is 2,6-difluorophen-1-yl which contains 1 to 3 further substituents, of which at least one is a radical of the formula II, IIa or IIb.
  • R 3 preferably has the same meaning as R 2 .
  • R 2 and R 3 are 2,6-difluorophen-1-yl to which a radical of the formula II, IIa, or IIb is bonded, and which may contain a further 1 or 2 identical or different substituents.
  • the group A is preferably bonded in the ortho-position to an F atom.
  • R 5 , R 6 , R 7 and R 8 are C 2 -C 8 dialkylamino, preferably C 2 -C 4 dialkylamino, for example dimethylamino, diethylamino, di-n-propylamino, di-n-butylamino or methylethylamino; bis[2-(C 1 -C 4 alkoxy)ethyl]amino, for example bis(2-methoxyethyl)amino or bis(2-ethoxyethyl)amino; morpholino; piperidino; N-methylpiperazino; pyrrolidino; quaternary C 3 -C 10 trialkylammonium, preferably C 3 -C 6 trialkylammonium, for example trimethylammonium, triethylammonium, dimethylethylammonium or dimethylpropylammonium; C 1 -C 12 alkoxy, preferably C 1 -C 12 alkoxy,
  • Alkyl R 5 , R 6 , R 7 and R 8 preferably contain 1 to 12 and particularly 1 to 8 C atoms. Examples are methyl, ethyl, and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tridecyl, tetradecyl, hexadecyl and octadecyl.
  • Alkenyl R 5 , R 6 , R 7 and R 8 preferably contain 2 to 4 C atoms.
  • Examples are vinyl, allyl, crotonyl, 2-methylprop-1-en-1-yl, but-1-en-1-yl, but-2-en-2-yl, but-2-en-1-yl, but-3-en-1-yl or -2-yl, or pent-1-en-1-yl.
  • Aryl R 5 , R 6 , R 7 and R 8 are in particular phenyl.
  • Aralkyl or alkaryl R 5 , R 6 , R 7 and R 8 may be, for example, benzyl, phenylethyl, phenylpropyl, methylphenyl, ethylphenyl, propylphenyl, dimethylphenyl and methylethylphenyl.
  • Alkaralkyl R 5 , R 6 , R 7 and R 8 may be, for example, methylbenzyl, ethylbenzyl, propylbenzyl, (methylphenyl)ethyl or dimethylbenzyl.
  • Cycloalkyl and cycloalkenyl R.sup. 5, R 6 , R 7 and R 8 are particularly cyclopentyl, cyclopentenyl, cyclohexyl or cyclohexenyl.
  • Alkanoyl R 5 , R 6 , R 7 and R 8 preferably contain 2 to 8, particularly 2 to 6, C atoms.
  • C 2 -C 12 Alkoxycarbonyl R 5 , R 6 , R 7 and R 8 are, in particular, C 2 -C 5 alkoxycarbonyl, for example methoxycarbonyl, ethoxycarbonyl or butoxycarbonyl.
  • R 5 , R 6 , R 7 and R 8 may be the --Ge(R 4 ) 3 and preferably --Si(R 4 ) 3 groups. In these groups, R 4 is preferably C 1 -C 12 alkyl, particularly C 1 -C 8 alkyl and in particular C 1 -C 4 alkyl.
  • the --Si(CH 3 ) 3 group is particularly preferred.
  • R 5 , R 6 , R 7 and R 8 are hydrogen or unsubstituted or substituted C 1 -C 12 alkyl, C 2 -C 5 alkenyl, C 7 -C 9 phenylalkyl, C 7 -C 10 alkylphenyl, phenyl, 2-furyl, C 5 - or C 6 cycloalkyl, C 5 - or C 6 cycloalkenyl, C 2 -C 8 alkanoyl, C 2 -C 5 alkoxycarbonyl, --CHO or --Si(R 4 ) 3 , in which R 4 is C 1 -C 8 alkyl or phenyl.
  • R 5 , R 6 , R 7 and R 8 are a hydrogen atom, or unsubstituted or substituted C 1 -C 8 alkyl, C 2 -C 4 alkenyl, benzyl, phenyl, 2-furyl, C 5 - or C 6 cycloalkyl, C 2 -C 6 alkanoyl, C 2 -C 5 alkoxycarbonyl, --CHO or --Si(R 4 ) 3 , in which R 4 is C 1 -C 4 alkyl.
  • R 9 may be substituted by C 1 -C 18 alkoxy, C 1 -C 18 alkylthio and C 1 -C 18 alkylsulfonyl, which preferably contain 1 to 12, particularly 1 to 6 and in particular 1 to 4, C atoms.
  • alkyl groups in these substituents are methyl, ethyl and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl and octadecyl.
  • R 9 is arylsulfonyl and alkarylsulfonyl, for example phenylsulfonyl, tolylsulfonyl or p-dodecylphenylsulfonyl.
  • R 9 may be linear or branched C 1 -C 20 alkyl, preferably C 1 -C 12 alkyl and particularly C 1 -C 8 alkyl. Examples are methyl, ethyl and the isomers of propyl, butyl, pentyl, hexyl, heptyl, octyl, nonyl, decyl, undecyl, dodecyl, tetradecyl, hexadecyl and octadecyl.
  • R 9 may be C 3 -C 8 cycloalkyl, preferably C 5 - C 7 cycloalkyl and particularly C 5 - C 6 cycloalkyl, for example cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cycloheptyl and cyclooctyl.
  • R 9 may be C 4 -C 20 cycloalkylalkyl or -alkylcycloalkyl, preferably C 6 -C 15 cycloalkylalkyl or -alkylcycloalkyl, the cycloalkyl preferably being cyclopentyl or cyclohexyl.
  • Examples are cyclopentyl- or cyclohexylmethyl, cyclopentyl- or cyclohexylethyl, cyclopentyl- or cyclohexylpropyl, cyclopentyl- or cyclohexylbutyl, methyl-, dimethyl-, ethyl-, n-propyl-, i-propyl-, n-butyl-, i-butyl- or t-butylcyclopentyl or -cyclohexyl.
  • R 9 may be C 5 -C 20 alkylcycloalkylalkyl, preferably C 7 -C 16 alkylcycloalkylalkyl, for example (methylcyclopentyl)methyl or -ethyl or (methylcyclohexyl)methyl or -ethyl.
  • R 9 may also be C 6 -C 14 aryl, preferably C 6 -C 10 aryl, for example naphthyl and particularly phenyl.
  • R 9 may also be C 7 -C 20 aralkyl or -alkaryl, preferably C 7 -C 16 aralkyl or -alkaryl.
  • the aryl here is preferably a phenyl radical. Examples are benzyl, phenylethyl, phenylpropyl, phenylbutyl, methylphenyl, ethylphenyl, propylphenyl and butylphenyl.
  • R 9 may also be C 8 -C 20 alkaralkyl, preferably C 8 -C 16 alkaralkyl, in which the aryl is preferably phenyl.
  • the aryl is preferably phenyl. Examples are methylbenzyl, (methylphenyl)ethyl, (methylphenyl)propyl, (methylphenyl)butyl, ethylbenzyl and propylbenzyl.
  • R 10 may have one of the meanings given for R 9 , including the preferences for R 9 .
  • R 10 may be C 1 -C 20 haloalkyl, preferably C 1 -C 12 haloalkyl and particularly C 1 -C 6 haloalkyl, it being possible for the alkyl group to be partially or fully substituted by halogen, preferably Cl and/or F.
  • Examples are chloromethyl, dichloromethyl, trichloromethyl, fluorodichloromethyl, difluorochloromethyl, trifluoromethyl, 2,2-dichloroethyl, 2,2-difluoroethyl, 1,1,1-trichloroethyl, 1,1,1-trifluoroethyl, pentafluoroethyl, chloropropyl, fluoropropyl, perfluoropropyl, chlorobutyl, fluorobutyl, perfluorobutyl, chloropentyl, perfluoropentyl and perfluorohexyl.
  • R 9 and R 10 may be linear or branched C 2 -C 20 alkenyl, preferably C 2 -C 12 alkenyl and particularly C 2 -C 6 alkenyl. Examples are vinyl, crotonyl, allyl, but-1-en-1-yl, but-1-en-4-yl, pent-1-en-1-yl, pent-2-en-2-yl, hex-1-en-yl, hex-3-en-3-yl and hex-1-en-6-yl.
  • R 10 may also be C 2 -C 20 alkyl, preferably C 2 -C 12 alkyl and particularly C 2 -C 6 alkyl which is interrupted by --CO--, for example acetylmethyl, propionylmethyl, acetylethyl and propionylethyl.
  • R 10 may also be the NR 13 R 14 group, in which R 13 and R 14 , independently of one another, have one of the meanings given for R 9 , including preferred embodiments.
  • R 13 and R 14 are preferably a hydrogen atom or C 1 -C 12 alkyl, particularly C 1 -C 6 alkyl, for example hexyl, pentyl, butyl, propyl and particularly ethyl or methyl.
  • R 9 and R 10 together may preferably be C 2 -C 8 alkylene which is unsubstituted or substituted by halogen, for example 1,2-ethylene, 1,3-propylene, 1,4-butylene, 1-dimethylethylene, 1-methyl-1-chloromethylethylene or 1-diethylethylene.
  • Y is preferably --CO--, --COO-- or --SO 2 --.
  • R 4 in the --Si(R 4 ) 3 group is particularly methyl.
  • Unsubstituted C 1 -C 20 alkanediyl Z may be linear or branched. It preferably has 1-8, in particular 1-4, C atoms. Examples of this are methylene, dimethylene, trimethylene, tetramethylene, pentamethylene, hexamethylene, octamethylene, 1,2-propylene, 1,2-butylene or 2,3-dimethyl-1,4-butylene. Z may be substituted by --COOR 4 , --CN or halogen. Examples of these are 2-methoxycarbonylethylene, 3-ethoxycarbonyl-1,2-propylene, 2-cyanoethylene, 1-chloroethylene or dichloromethylene.
  • Preferred titanocenes of the formula I are those in which R 2 and R 3 are substituted by a radical of the formula II, in which R 5 , R 6 , R 7 and R 8 , independently of one another, are hydrogen, C 1 -C 12 alkyl, C 2 -C 5 alkenyl, C 7 -C 9 phenylalkyl, C 7 -C 10 alkylphenyl, phenyl, 2-furyl, C 5 - or C 6 cycloalkyl, C 5 - or C 6 cycloalkenyl, C 2 -C 8 alkanoyl, C 2 -C 5 alkoxycarbonyl, --CHO or --Si(R 4 ) 3 , in which R 4 is C 1 -C 8 alkyl or phenyl, each of which is unsubstituted or substituted by C 2 -C 8 dialkylamino, bis(2-methoxyethyl)amino, morpholino, piperidino, C
  • a further preferred class of titanocenes of the formula I in which R 2 and R 3 are substituted by a radical of the formula II is formed by compounds in which R 5 , R 6 , R 7 and R 8 , independently of one another, are hydrogen, C 1 -C 8 alkyl, C 2 -C 4 alkenyl, phenyl, 2-furyl or --Si(R 4 ) 3 , in which R 4 is C 1 -C 4 alkyl, each of which is unsubstituted or substituted by C 2 -C 8 dialkylamino, morpholino, C 1 -C 4 alkoxy, 1,3-dioxolan-2-yl or cyano, and Z is unsubstituted C 1 -C 4 alkanediyl, in particular those in which R 5 , R 6 , R 7 and R 8 , independently of one another, are hydrogen or C 1 -C 4 alkyl, and those in which R 6 and R 7 are hydrogen.
  • a further preferred class of titanocenes of the formula I is formed by compounds in which R 2 and R 3 are substituted by a group of the formula IIa, in which Y is --CO--, --CS--, --COO-- or --SO 2 --, R 9 is hydrogen, C 1 -C 12 alkyl, C 2 -C 5 alkenyl, C 5 -C 8 cycloalkyl, C 6 -C 18 cycloalkylalkyl, C 6 -C 18 alkylcycloalkyl, C 7 -C 18 alkylcycloalkylalkyl, C 7 -C 16 aralkyl or C 8 -C 16 alkaralkyl, each of which is unsubstituted or substituted by C 1 -C 12 alkoxy or tetrahydrofuryl, R 10 has one of the meanings given for R 9 or is C 6 -C 10 aryl, C 6 -C 10 haloaryl, C 7 -C 18 alkaryl or
  • R 9 is hydrogen, C 1 -C 12 alkyl, cyclohexyl, cyclohexylmethyl, 2-tetrahydrofurylmethyl, C 2 -C 8 alkoxyalkyl, allyl or C 7 -C 9 aralkyl
  • R 10 is C 1 -C 18 alkyl, C 1 -C 4 haloalkyl, cyclohexyl, C 6 -C 10 aryl, halophenyl or C 7 -C 18 alkaryl, or R 9 and R 10 together are C 2 -C 6 alkylene
  • Y is --CO--, --COO-- or --SO 2 -- or the radical --Y--R 10 is a --CO--NHR 13 , --CS--NHR 13 , --CO--NR 13 R 14 or --SO 2 --NR 13 R 14 group, in which R 13 is C 1 -C 12 alkyl or phenyl, R 14 is C 1 -C 12
  • R 10 and R 11 together are C 2 -C 8 alkanediyl, C 2 -C 8 alkenediyl, C 6 -C 14 arenediyl, cyclohexanediyl or C 7 -C 12 bicycloalkanediyl, Y is --CO--, and Z is unsubstituted C 1 -C 4 alkanediyl.
  • the titanocenes of the formula I can be prepared by known processes or analogously to known processes by reacting 1 mole of a compound of the formula IV ##STR6## in which R 1 is as defined above and X is halogen, particularly chlorine, with one mole of LiR 2 and with one mole of LiR 3 or with 2 moles of LiR 2 , R 2 and R 3 being as defined above, and then isolating the compounds of the formula I in a manner known per se.
  • Lithium compounds LiR 2 and LiR 3 are novel. They can be prepared, for example, by processes known per se by reacting butyllithium with HR 2 or HR 3 . This is described in greater detail in the examples below.
  • the compounds HR 2 and HR 3 can be prepared analogously to the processes known per se.
  • the appropriate aminoalkylfluoroarenes are first prepared, for example by reducing the corresponding nitriles.
  • the primary amines can be converted into pyrrole derivatives which contain a radical of the formula II using 1,4-dicarbonyl compounds or using 2,5-dimethoxytetrahydrofuran.
  • the radical R 9 can be introduced by reductive amination of the corresponding aldehydes or ketones.
  • the radicals R 10 Y-- and R 11 Y-- can be introduced by means of the halogen compounds R 10 --Y--X and R 11 --Y--X or by means of the acid anhydrides (R 10 Y) 2 O.
  • the preparation of the metallocenes of the formula I from the compounds HR 2 and HR 3 is generally carried out in the presence of inert solvents, for example hydrocarbons or ethers, and under a protective-gas atmosphere.
  • LiR 2 or LiR 3 is first prepared by reacting HR 2 or HR 3 respectively with butyllithium in an ether as solvent, for example tetrahydrofuran, at temperatures around -78° C.
  • the appropriate titanocene dihalide is then added to the cooled reaction mixture, the cooling is removed, and the mixture is allowed to warm to room temperature.
  • the reaction mixture is then filtered, if necessary after addition of solvents, and the titanocene according to the invention is isolated from the solution by precipitation or evaporation of the solvent.
  • a mixture of HR 2 and titanocene chloride in tetrahydrofuran is reacted at -25° to -10° C. with a solution of a lithium amide, for example with lithium diisopropylamide.
  • the titanocene is isolated in the customary manner after removal of the LiCl formed.
  • the titanocenes are generally crystalline, usually orange compounds which are distinguished by high thermal stability and only decompose at high temperatures. No decomposition is observed either under the action of air or under the action of water.
  • the compounds can be dissolved, even in relatively high amounts, in curable compositions, and therefore offer valuable applicational properties.
  • the compounds are also readily soluble in solvents, and can be incorporated in the form of solutions into curable compositions, after which the solvent is removed if necessary.
  • the invention furthermore relates to a radiation-polymerizable composition containing (a) at least one non-volatile, monomeric, oligomeric or polymeric compound containing at least one polymerizable ethylenically unsaturated double bond, and (b) at least one titanocene of the formula I as photoinitiator.
  • compositions may contain further photoinitiators (c) which are different from (b), for example those of the benzophenone, benzoin alkyl ether, benzil ketal, 4-aroyl-1,3-dioxolane, dialkoxyacetophenone, ⁇ -hydroxy- or ⁇ -aminoacetophenone, ⁇ -hydroxycycloalkyl phenyl ketone type, or mixtures thereof.
  • photoinitiators (c) which are different from (b), for example those of the benzophenone, benzoin alkyl ether, benzil ketal, 4-aroyl-1,3-dioxolane, dialkoxyacetophenone, ⁇ -hydroxy- or ⁇ -aminoacetophenone, ⁇ -hydroxycycloalkyl phenyl ketone type, or mixtures thereof.
  • the advantage is that lower amounts of the titanocenes according to the invention can be used and nevertheless equal or improved photosensitivities can be achieved.
  • titanocenes depends essentially on economic points of view, their solubilities and on the desired sensitivity. In general, 0.01 to 20, preferably 0.05-10 and particularly 0.1 to 5,% by weight are used, relative to component (a).
  • Esters of ethylenically unsaturated carboxylic acids and polyols or polyepoxides, and polymers containing ethylenically unsaturated groups in the chain or in side groups for example unsaturated polyesters, polyamides and polyurethanes, and copolymers thereof, polybutadiene and butadiene copolymers, polyisoprene and isoprene copolymers, polymers and copolymers containing (meth)acrylic groups in the side chains, and mixtures of two or more such polymers, for example, are particularly suitable.
  • unsaturated carboxylic acids are acrylic acid, methacrylic acid, crotonic acid, itaconic acid, cinnamic acid, unsaturated fatty acids, such as linolenic acid or oleic acid.
  • Acrylic acid and methyacrylic acid are preferred.
  • Suitable polyols are aromatic and particularly aliphatic and cycloaliphatic polyols.
  • aromatic polyols are hydroquinone, 4,4'-dihydroxydiphenyl, 2,2-di(4-hydroxyphenyl)propane, and novolaks and resols.
  • polyepoxides are those based on the polyols mentioned, particularly on the aromatic polyols and epichlorohydrin.
  • polymers or copolymers which contain hydroxyl groups in the polymer chain or side groups for example polyvinyl alcohol and copolymers thereof, or hydroxyalkyl polymethacrylates or copolymers thereof, are also suitable as polyols.
  • Further suitable polyols are oligoesters containing hydroxyl end groups.
  • Examples of aliphatic and cycloaliphatic polyols are alkylene diols preferably having 2 to 12 C atoms, such as ethylene glycol, 1,2- or 1,3-propanediol, 1,2-, 1,3- or 1,4-butanediol, pentanediol, hexanediol, octanediol, dodecanediol, diethylene glycol, triethylene glycol, polyethylene glycols having molecular weights of, preferably, 200 to 1500, 1,3-cyclopentanediol, 1,2-, 1,3- or 1,4-cyclohexanediol, 1,4-dihydroxymethylcyclohexane, glycerol, tris( ⁇ -hydroxyethyl)amine, trimethylolethane, trimethylolpropane, pentaerythritol, dipentaerythritol and sorbitol.
  • the polyols may be partially or fully esterified with one or different unsaturated carboxylic acids, it being possible, in partial esters, for the free hydroxyl groups to be modified, for example etherified or esterified with other carboxylic acids.
  • esters are: trimethylolpropane triarcrylate, trimethylolethane triacrylate, trimethylolpropane trimethacrylate, trimethylolethane trimethacrylate, tetramethylene glycol dimethacrylate, triethylene glycol dimethacrylate, tetraethylene glycol diacrylate, pentaerythritol diacrylate, pentaerythritol triacrylate, pentaerythritol tetraacrylate, dipentaerythritol diacrylate, dipentaerythritol triacrylate, dipentaerythritol tetraacrylate, dipentaerythritol pentaacrylate, dipentaerythritol hexaacrylate, tripentaerythritol octaacrylate, pentaerythritol dimethacrylate, pentaerythritol trimethacrylate, dipentaerythr
  • Compounds which are suitable as component (a) are also the amides of identical or different unsaturated carboxylic acids of aromatic, cycloaliphatic and aliphatic polyamines preferably having 2 to 6, particularly 2 to 4, amino groups.
  • polyamines are ethylenediamine, 1,2- or 1,3-propylenediamine, 1,2-, 1,3,- or 1,4-butylenediamine, 1,5-pentylenediamine, 1,6-hexylenediamine, octylenediamine, dodecylenediamine, 1,4-diaminocyclohexane, isophoronediamine, phenylenediamine, bisphenylenediamine, di- ⁇ -aminoethyl ether, diethylenetriamine, triethylenetetramine, di( ⁇ -aminoethoxy)- or di( ⁇ -aminopropoxy)ethane.
  • Further suitable polyamines are polymers and copolymers containing amino groups in the side chain
  • unsaturated amides of this type are: methylene bisacrylamide, 1,6-hexamethylene bisacrylamide, diethylenetriamine trismethacrylamide, bis(methacrylamidopropoxy)ethane, ⁇ -methacrylamidoethyl methacrylate and N-[( ⁇ -hydroxyethoxy)ethyl]acrylamide.
  • Suitable unsaturated polyesters and polyamides are derived, for example, from maleic acid and diols or diamines.
  • Maleic acid may be partially replaced by other dicarboxylic acids. They can be employed together with ethylenically unsaturated comonomers, for example styrene.
  • Polyesters and polyamides may also be derived from dicarboxylic acids and ethylenically unsaturated diols or diamines, particularly from those having relatively long chains with, for example, 6 to 20 C atoms.
  • Examples of polyurethanes are those built up from saturated or unsaturated diisocyanates and unsaturated or saturated diols.
  • Polybutadiene and polyisoprene and copolymers thereof are known.
  • suitable comonomers are olefins, such as ethylene, propene, butene, hexene, (meth)acrylates, acrylonitrile, styrene or vinyl chloride.
  • Polymers containing (meth)acrylate groups in the side chain are likewise known.
  • They may be, for example, products of the reaction of epoxy resins based on novolak with (meth)acrylic acid, homopolymers or copolymers of polyvinyl alcohol or hydroxyalkyl derivatives thereof which have been esterified with (meth)acrylic acid, or homopolymers and copolymers of (meth)acrylates which have been esterified with hydroxyalkyl (meth)acrylates.
  • Binders may also be added to the compositions according to the invention, which is particularly expedient if the photopolymerizable compounds are liquid or viscous substances.
  • the amount of binder can be, for example, 5-95, preferably 10-90 and particularly 50-90, % by weight, relative to the total composition.
  • the choice of binder depends on the area of application and properties required for this purpose, such as ability to be developed in aqueous and organic solvent systems, adhesion to substrates and oxygen sensitivity.
  • binders are polymers having a molecular weight of from about 5000-2,000,000, preferably 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5000-2,000,000, preferably 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5000-2,000,000, preferably 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5000-2,000,000, preferably 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5000-2,000,000, preferably 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5000-2,000,000, preferably 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5000-2,000,000, preferably 10,000 to 1,000,000.
  • suitable binders are polymers having a molecular weight of from about 5000-2,000,000, preferably 10,000 to 1,000,000.
  • suitable binders are polymers
  • compositions according to the invention are suitable as coating agents for substrates of all types, for example wood, paper, ceramics, plastics, such as polyester and cellulose acetate films, and metals, such as copper and aluminium, in which a protective layer or photographic image is to be applied by photopolymerization.
  • the present invention furthermore relates to the coated substrates and to a process for applying photographic images to the substrates.
  • the coated substrates may also be used as recording material for holograms (volume/phase diagram), in which case it is advantageous that wet development is not necessary for this purpose.
  • the substrates can be coated by applying a liquid composition, a solution or suspension to the substrate.
  • Liquid compositions without solvents are preferred.
  • Liquid mixtures comprising liquid to solid photoinitiators and liquid titanocenes or liquid photoinitiators and syrupy to solid titanocenes are particularly advantageous. These mixtures offer applicational advantages and are distinguished by high stability on storage in the dark.
  • 4-aroyl-1,3-dioxolanes are:
  • dialkoxyacetophenones examples are:
  • ⁇ -hydroxycycloalkyl phenyl ketones are:
  • the weight ratio of components (b):(c) can be from 1:1 to 30:1, preferably 5:1 to 15:1.
  • the choice of solvent and the concentration depend principally on the nature of the composition and on the coating process.
  • the composition is applied uniformly to a substrate by known coating processes, for example by dipping, knife coating, curtain coating, electrophoresis, brushing, spraying or reverse-roll coating.
  • the amount applied (coating thickness) and the nature of the substrate (coating base) depend on the desired area of application.
  • the coating bases used are: for photographic information recording, for example films made from polyester or cellulose acetate or plastic-coated papers; for offset printing plates, especially treated aluminium; and for the production of printed circuits, copper-laminated laminates.
  • the coating thicknesses for photographic materials and offset printing plates are generally about 0.5 to about 10 ⁇ m, for printed circuits, generally 1 to about 100 ⁇ m. If solvents are also used, they are removed after coating.
  • the titanocenes according to the invention may also be used as photoinitiators in photocurable compositions for dental applications. They give, with short irradiation times, materials of high strength and low degree of residual unsaturated components. By irradiating dental compositions based on olefinically unsaturated resins, inorganic fillers and titanocene photoinitiators, hardening depths of several millimeters can be achieved within a few seconds using commercial light sources for dental applications. Examples of compositions for dental materials which can be cured using compounds according to the invention, as well as further details on binders, fillers, further additives and application methods, are given, for example, in EP-A-334,338 and DE-A-3,801,511.
  • Photocurable compositions as are used for various purposes usually contain a number of other additives in addition to the photopolymerizable compounds and photoinitiators.
  • thermal inhibitors which are intended to protect against premature polymerization, particularly during preparation of the compositions by mixing the components.
  • hydroquinone, hydroquinone derivatives, p-methoxyphenol, ⁇ -naphthols or sterically hindered phenols, for example 2,6-di(tert-butyl)-p-cresol are used for example.
  • small amounts of UV absorbers may be added, for example those of the benzotriazole, benzophenone or oxalanilide type. It is also possible to add light screens of the sterically hindered amine type (HALS).
  • HALS sterically hindered amine type
  • copper compounds such as copper naphthenate, stearate or octanoate
  • phosphorus compounds such as triphenylphosphine, tributylphosphine, triethyl phosphite, triphenyl phosphite or tribenzyl phosphite
  • quaternary ammonium compounds such as tetramethylammonium chloride or trimethylbenzylammonium chloride, or hydroxylamine derivatives, for example N-diethylhydroxylamine, may be added.
  • paraffin or similar waxy substances are frequently added to photocurable mixtures. Due to low solubility in the polymer, these float at the beginning of the polymerization and form a transparent surface layer which prevents ingress of air.
  • photosensitizers which absorb in certain wavelengths and pass the absorbed energy to the initiators or themselves function as an additional initiator. Examples of these are, in particular, thioxanthone, anthracene, anthraquinone and coumarine derivatives.
  • accelerators of the amine type which are particularly important in pigmented preparations since they act as chain-transfer agents. Examples of these are N-methyldiethanolamine, triethylamine, ethyl p-dimethylaminobenzoate or Michler's ketone. The action of the amines can be reinforced by adding aromatic ketones of the benzophenone type.
  • Further customary accelerators are 1,3,4-thiadiazole derivatives, for example 2-mercapto-5-methylthio-1,3,4-thiadiazole.
  • additives examples include fillers, pigments, dyes, adhesives, wetting agents and flow-control agents.
  • the photocurable compositions according to the invention are also highly suitable for the production of printing plates, in particular flexographic printing plates.
  • mixtures of soluble, linear polyamides or of styrene-butadiene rubber with photopolymerizable monomers, for example acrylamides or acrylates, and a photoinitiator are used.
  • Films and plates made from these systems are exposed over the negative (or positive) of the print master, and the non-cured areas are subsequently eluted using a solvent.
  • a further area of application for photocuring is metal coating, for example in the painting of metal sheeting for tubes, cans or bottle caps, and the photocuring of plastic coatings, for example of PVC-based floor coverings or wall coverings.
  • Examples of the photocuring of paper coatings are the clear coating of labels, record sleeves or book covers.
  • the use of the photocurable compositions is also important for imaging processes and for optical production of information carriers.
  • developer a solvent
  • the exposed areas are crosslinked and polymeric and are thus insoluble and remain on the backing.
  • visible images are produced.
  • the backing is a metallized layer, the metal can be removed at the unexposed areas by etching after exposure and development or thickened by electroplating. In this way, printed circuits and photoresists can be produced.
  • Light sources having a high proportion of short-wave light are suitable for the exposure.
  • suitable technical equipment and various types of lamps are available for this purpose. Examples are carbon arc lamps, xenon arc lamps, mercury vapour lamps, metal halogen lamps, fluorescent lamps, argon lamps or photographic floodlamps.
  • laser light sources have also been used. These have the advantage that photomasks are not necessary; the controlled laser beam writes directly on the photocurable coating.
  • the organic phase is separated off, dried using magnesium sulfate, filtered and evaporated on a vacuum rotary evaporator.
  • the turbid oil is taken up in 300 ml of petroleum ether, clarified and re-evaporated. 124.7 g of a colourless liquid which is purified by fractional distillation at 125°-127° C. and 15 mbar are obtained. 85.3 g (60% or theory) of pure product are obtained.
  • the solution is then added to a mixture of 100 ml of ethyl acetate, 100 ml of water and 1.3 g (0.022 mol) of acetic acid, and the mixture is stirred.
  • the orange suspension is filtered through Hyflo.
  • the two phases of the filtrate are separated from one another.
  • the organic phase is dried using magnesium sulfate and evaporated in a vacuum rotary evaporator at 20 mbar and a water-bath temperature of 50° C. 7.9 g of a dark-red oil, which is purified by flash chromatography using hexane/ethyl acetate (9:1) as solvent, are obtained. 3.3 g of an orange-red glassy resin are obtained.
  • Portions of this composition are in each case mixed with 0.3% (relative to the solids content) of photoinitiator. All operations are carried out under a red light or yellow light.
  • the samples mixed with initiator are applied in a thickness of 150 ⁇ m to a 200 ⁇ m aluminium foil (10 ⁇ 15 cm).
  • the solvent is removed by warming at 60° C. for 15 minutes in a circulation oven.
  • a 76 ⁇ m thick polyester film is placed on the liquid coating, and this is covered by a standardized test negative with 21 steps of different optical density (Stouffer wedge). This is covered by a second polyester film, and the resultant laminate is fixed onto a metal plate.
  • the sample is exposed with a 5 kW metal halide lamp at a distance of 30 cm for 10 seconds for a first test series, for 20 seconds for a second test series and for 40 seconds for a third test series.
  • developer A contains 15 g of sodium metasilicate.H 2 O; 0.16 g of KOH; 3 g of polyethylene glycol 6000; 0.5 g of levulinic acid and 1000 g of deionized water.
  • a photocurable composition is prepared by mixing the following components:
  • the samples mixed with initiator are applied in a thickness of 200 ⁇ m to a 200 ⁇ m aluminium foil (10 ⁇ 15 cm).
  • the solvent is removed by warming at 60° C. for 15 minutes in a circulation oven.
  • a 76 ⁇ m thick polyester film is placed on the liquid coating, and this is covered by a standardized test negative with 21 steps of different optical density (Stouffer wedge). This is covered by a second polyester film, and the resultant laminate is fixed onto a metal plate.
  • the sample is exposed with a 5 kW metal halide lamp at a distance of 30 cm for 10 seconds for a first test series, for 20 seconds for a second test series and for 40 seconds for a third test series.
  • the exposed coating is developed in an ultrasound bath for 240 seconds using developer A and subsequently dried at 60° for 15 minutes in a circulation oven.
  • the sensitivity of the initiator system used is characterized by indicating the final wedge step imaged without adhesion. The higher the number of steps, the more sensitive the system. An increase by two steps indicates an approximate doubling of the curing rate. The results are given in Table 2.

Landscapes

  • Chemical & Material Sciences (AREA)
  • Organic Chemistry (AREA)
  • Physics & Mathematics (AREA)
  • Spectroscopy & Molecular Physics (AREA)
  • Polymers & Plastics (AREA)
  • Medicinal Chemistry (AREA)
  • Inorganic Chemistry (AREA)
  • Chemical Kinetics & Catalysis (AREA)
  • Health & Medical Sciences (AREA)
  • General Physics & Mathematics (AREA)
  • Paints Or Removers (AREA)
  • Pyrrole Compounds (AREA)
  • Coating Of Shaped Articles Made Of Macromolecular Substances (AREA)
  • Photoreceptors In Electrophotography (AREA)
  • Inks, Pencil-Leads, Or Crayons (AREA)
  • Polymerisation Methods In General (AREA)
  • Materials For Photolithography (AREA)
  • Non-Silver Salt Photosensitive Materials And Non-Silver Salt Photography (AREA)
US07/527,989 1989-06-01 1990-05-23 Novel nitrogen-containing titanocenes, and the use thereof Expired - Fee Related US5068371A (en)

Applications Claiming Priority (2)

Application Number Priority Date Filing Date Title
CH2075/89 1989-06-01
CH207589 1989-06-01

Publications (1)

Publication Number Publication Date
US5068371A true US5068371A (en) 1991-11-26

Family

ID=4225317

Family Applications (1)

Application Number Title Priority Date Filing Date
US07/527,989 Expired - Fee Related US5068371A (en) 1989-06-01 1990-05-23 Novel nitrogen-containing titanocenes, and the use thereof

Country Status (5)

Country Link
US (1) US5068371A (ja)
EP (1) EP0401166B1 (ja)
JP (1) JP2818968B2 (ja)
CA (1) CA2017934C (ja)
DE (1) DE59008501D1 (ja)

Cited By (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5340701A (en) * 1992-04-09 1994-08-23 Ciba-Geigy Corporation Fluorine-free titanocenes and the use thereof
US5646323A (en) * 1994-09-09 1997-07-08 Phillips Petroleum Company Process for preparing metallocene compounds
KR19980024606A (ko) * 1996-09-13 1998-07-06 사사끼 요시오 가시광 레이저 경화성 조성물
US6010824A (en) * 1992-11-10 2000-01-04 Tokyo Ohka Kogyo Co., Ltd. Photosensitive resin composition containing a triazine compound and a pre-sensitized plate using the same, and photosensitive resin composition containing acridine and triazine compounds and a color filter and a pre-sensitized plate using the same
US6054251A (en) * 1996-09-25 2000-04-25 Kansai Paint Co., Ltd. Photopolymerizable composition
US6265458B1 (en) * 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US20020115885A1 (en) * 2001-02-16 2002-08-22 Walter Lange Polyhalogen-substituted cinnamic acids and cinnamic acid derivatives and a process for the preparation of polyhalogen-substituted cinnamic acids and cinnamic acid derivatives
US6880296B1 (en) 1999-12-17 2005-04-19 S & C Polymer Silicon- Und Composite-Spezialitaten Gmbh Photoinitiator system with titanocene initiators
US6936384B2 (en) 2002-08-01 2005-08-30 Kodak Polychrome Graphics Llc Infrared-sensitive composition containing a metallocene derivative
US20070197597A1 (en) * 2004-03-02 2007-08-23 Sanofi-Aventis Deutschland Gmbh Process for the preparation of tryptase inhibitors
US20120205140A1 (en) * 2011-02-14 2012-08-16 Deepak Shukla Articles with photocurable and photocured compositions

Families Citing this family (11)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
JP2551232B2 (ja) * 1990-11-22 1996-11-06 日立化成工業株式会社 新規な光開始剤系及びこれを用いた光重合性組成物
FR2686607B1 (fr) * 1992-01-24 1995-03-17 Celliose Lobo Entreprise Systeme photosensible sous irradiation visible et ultra-violette pour compositions filmogenes pigmentees photoreticulables.
CN1062275C (zh) * 1995-12-15 2001-02-21 化学工业部北京化工研究院 用于乙烯聚合的茂金属催化体系及其应用
DE69620723T2 (de) 1995-12-22 2002-12-05 Mitsubishi Chem Corp Fotopolymerisierbare Zusammensetzung für einen Farbfilter, Farbfilter und Flüssigkristallanzeigevorrichtung
JP4130030B2 (ja) 1999-03-09 2008-08-06 富士フイルム株式会社 感光性組成物および１，３−ジヒドロ−１−オキソ−２ｈ−インデン誘導体化合物
EP1571150A1 (en) * 2004-03-02 2005-09-07 Aventis Pharma Deutschland GmbH Process for the preparation of tryptase inhibitors
JP4452572B2 (ja) 2004-07-06 2010-04-21 富士フイルム株式会社 感光性組成物およびそれを用いた画像記録方法
JP5089866B2 (ja) 2004-09-10 2012-12-05 富士フイルム株式会社 平版印刷方法
JP5102454B2 (ja) 2006-03-03 2012-12-19 富士フイルム株式会社 チタノセン系化合物、感光性組成物、及び感光性転写シート
EP2154162B1 (en) 2007-05-23 2019-07-17 Showa Denko K.K. Reactive urethane compound having ether bond, curable composition and cured material
JP4890408B2 (ja) 2007-09-28 2012-03-07 富士フイルム株式会社 重合性組成物及びそれを用いた平版印刷版原版、アルカリ可溶性ポリウレタン樹脂、並びに、ジオール化合物の製造方法

Citations (8)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4590287A (en) * 1983-02-11 1986-05-20 Ciba-Geigy Corporation Fluorinated titanocenes and photopolymerizable composition containing same
US4713401A (en) * 1984-12-20 1987-12-15 Martin Riediker Titanocenes and a radiation-polymerizable composition containing these titanocenes
EP0256981A2 (de) * 1986-08-01 1988-02-24 Ciba-Geigy Ag Titanocene und deren Verwendung
EP0318893A2 (de) * 1987-12-01 1989-06-07 Ciba-Geigy Ag Titanocene, deren Verwendung und N-substituierte Fluoraniline
EP0318894A2 (de) * 1987-12-01 1989-06-07 Ciba-Geigy Ag Titanocene, deren Verwendung und N-substituierte Pyrrole
US4857654A (en) * 1986-08-01 1989-08-15 Ciba-Geigy Corporation Titanocenes and their use
US4960746A (en) * 1986-11-26 1990-10-02 Ciba-Geigy Corporation Liquid photoinitiator mixtures
US4973722A (en) * 1986-11-10 1990-11-27 Ciba-Geigy Corporation Process for preparing organometallic compounds

Patent Citations (9)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US4590287A (en) * 1983-02-11 1986-05-20 Ciba-Geigy Corporation Fluorinated titanocenes and photopolymerizable composition containing same
US4910121A (en) * 1983-02-11 1990-03-20 Ciba-Geigy Corporation Photopolymerizable composition containing metallocenes
US4713401A (en) * 1984-12-20 1987-12-15 Martin Riediker Titanocenes and a radiation-polymerizable composition containing these titanocenes
EP0256981A2 (de) * 1986-08-01 1988-02-24 Ciba-Geigy Ag Titanocene und deren Verwendung
US4857654A (en) * 1986-08-01 1989-08-15 Ciba-Geigy Corporation Titanocenes and their use
US4973722A (en) * 1986-11-10 1990-11-27 Ciba-Geigy Corporation Process for preparing organometallic compounds
US4960746A (en) * 1986-11-26 1990-10-02 Ciba-Geigy Corporation Liquid photoinitiator mixtures
EP0318893A2 (de) * 1987-12-01 1989-06-07 Ciba-Geigy Ag Titanocene, deren Verwendung und N-substituierte Fluoraniline
EP0318894A2 (de) * 1987-12-01 1989-06-07 Ciba-Geigy Ag Titanocene, deren Verwendung und N-substituierte Pyrrole

Non-Patent Citations (2)

* Cited by examiner, † Cited by third party
Title
C. Tamborski et al., J. Organomet. Chem., 4, 446 (1965). *
M. A. Chaudhari, et al., J. Organomet. Chem., 2, 206(1964). *

Cited By (18)

* Cited by examiner, † Cited by third party
Publication number Priority date Publication date Assignee Title
US5340701A (en) * 1992-04-09 1994-08-23 Ciba-Geigy Corporation Fluorine-free titanocenes and the use thereof
US6010824A (en) * 1992-11-10 2000-01-04 Tokyo Ohka Kogyo Co., Ltd. Photosensitive resin composition containing a triazine compound and a pre-sensitized plate using the same, and photosensitive resin composition containing acridine and triazine compounds and a color filter and a pre-sensitized plate using the same
US5646323A (en) * 1994-09-09 1997-07-08 Phillips Petroleum Company Process for preparing metallocene compounds
KR19980024606A (ko) * 1996-09-13 1998-07-06 사사끼 요시오 가시광 레이저 경화성 조성물
US5939148A (en) * 1996-09-13 1999-08-17 Kansai Paint Co., Ltd. Visible laser-curable composition
US6054251A (en) * 1996-09-25 2000-04-25 Kansai Paint Co., Ltd. Photopolymerizable composition
US6265458B1 (en) * 1998-09-28 2001-07-24 Kimberly-Clark Worldwide, Inc. Photoinitiators and applications therefor
US6880296B1 (en) 1999-12-17 2005-04-19 S & C Polymer Silicon- Und Composite-Spezialitaten Gmbh Photoinitiator system with titanocene initiators
US20020115885A1 (en) * 2001-02-16 2002-08-22 Walter Lange Polyhalogen-substituted cinnamic acids and cinnamic acid derivatives and a process for the preparation of polyhalogen-substituted cinnamic acids and cinnamic acid derivatives
US6956129B2 (en) 2001-02-16 2005-10-18 Bayer Aktiengesellschaft Polyhalogen-substituted cinnamic acids and cinnamic acid derivatives and a process for the preparation of polyhalogen-substituted cinnamic acids and cinnamic acid derivatives
US20050234264A1 (en) * 2001-02-16 2005-10-20 Walter Lange Polyhalogen-substituted cinnamic acids and cinnamic acid derivatives and a process for the preparation of polyhalogen-substituted cinnamic acids and cinnamic acid derivatives
US7381832B2 (en) 2001-02-16 2008-06-03 Lanxess Deutschland Gmbh Polyhalogen-substituted cinnamic acids and cinnamic acid derivatives and a process for the preparation of polyhalogen-substituted cinnamic acids and cinnamic acid derivatives
US20080200731A1 (en) * 2001-02-16 2008-08-21 Walter Lange Polyhalogen-substituted cinnamic acids and cinnamic acid derivatives and a process for the preparation of polyhalogen-substituted cinnamic acids and cinnamic acid derivatives
US6936384B2 (en) 2002-08-01 2005-08-30 Kodak Polychrome Graphics Llc Infrared-sensitive composition containing a metallocene derivative
US20070197597A1 (en) * 2004-03-02 2007-08-23 Sanofi-Aventis Deutschland Gmbh Process for the preparation of tryptase inhibitors
US20110015400A1 (en) * 2004-03-02 2011-01-20 Sanofi-Aventis Deutschland Gmbh Process for the preparation of tryptase inhibitors
US20120205140A1 (en) * 2011-02-14 2012-08-16 Deepak Shukla Articles with photocurable and photocured compositions
US8816211B2 (en) * 2011-02-14 2014-08-26 Eastman Kodak Company Articles with photocurable and photocured compositions

Also Published As

Publication number Publication date
EP0401166A3 (de) 1991-02-06
EP0401166B1 (de) 1995-02-22
JPH0327393A (ja) 1991-02-05
EP0401166A2 (de) 1990-12-05
CA2017934C (en) 2001-01-02
CA2017934A1 (en) 1990-12-01
JP2818968B2 (ja) 1998-10-30
DE59008501D1 (de) 1995-03-30

Similar Documents

Publication Publication Date Title
US5068371A (en) Novel nitrogen-containing titanocenes, and the use thereof
RU2086555C1 (ru) Титаноцены
US4970136A (en) Titanocenes and their use
US5192642A (en) Oxygen-containing titanocenes, and the use thereof
JP2747831B2 (ja) チタノセンおよびそれを含有する光重合性組成物
US4963470A (en) Titanocenes and their use
US4590287A (en) Fluorinated titanocenes and photopolymerizable composition containing same
US5932393A (en) Borate photoinitiators from monoboranes
US4713401A (en) Titanocenes and a radiation-polymerizable composition containing these titanocenes
JPH1029965A (ja) α−アミノアセトフェノン誘導体

Legal Events

Date Code Title Description
AS Assignment

Owner name: CIBA-GEIGY CORPORATION, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST.;ASSIGNORS:STEINER, EGINHARD;BEYELER, HARRY;HUSLER, RINALDO;REEL/FRAME:005756/0032

Effective date: 19900425

FEPP Fee payment procedure

Free format text: PAYOR NUMBER ASSIGNED (ORIGINAL EVENT CODE: ASPN); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 4

AS Assignment

Owner name: CIBA SPECIALTY CHEMICALS CORPORATION, NEW YORK

Free format text: ASSIGNMENT OF ASSIGNORS INTEREST;ASSIGNOR:CIBA-GEIGY CORPORATION;REEL/FRAME:008519/0545

Effective date: 19961227

REFU Refund

Free format text: REFUND - PAYMENT OF MAINTENANCE FEE, 8TH YEAR, LARGE ENTITY (ORIGINAL EVENT CODE: R184); ENTITY STATUS OF PATENT OWNER: LARGE ENTITY

FPAY Fee payment

Year of fee payment: 8

REMI Maintenance fee reminder mailed
LAPS Lapse for failure to pay maintenance fees
FP Lapsed due to failure to pay maintenance fee

Effective date: 20031126

STCH Information on status: patent discontinuation

Free format text: PATENT EXPIRED DUE TO NONPAYMENT OF MAINTENANCE FEES UNDER 37 CFR 1.362